2,2{40 -diacylamino-1,1{40 -dianthraquinonyls

ABSTRACT

2,2&#39;&#39;-DIACYLAMINO-1,1&#39;&#39;-DIANTHRAQUINONYLS HAVING THE GENERAL FORMULA:   IN WHICH R denotes alkyl having one to six carbon atoms or substituted or unsubstituted aryl and to a method for the production of the compounds (I). The compounds (I) may be prepared by reaction of 1-halo-2-acylaminoanthraquinones having the formula:   IN WHICH R has the above meanings and Hal denotes a chlorine or bromine atom with copper powder in a solvent which contains the grouping -N-CO-. The compounds (I) represent a valuable intermediate for the manufacture of dyes, e.g. flavanthrene.

Waited States Patent 1 Schuhmacher 1 Mar. 27, 1973 5412',2'-DIACYLAMINO-1,1-

DIANTHRAQUINONYLS [75] Inventor: Alfred Schuhmacher, Ludwigshafen,

Germany [73] Assignee: Badische Anilin- & Soda-FabrikAktienges'ellschaft, Ludwigshafen am Rhine, Germany [22] Filed: Aug. 26,1970 [21] Appl. No.: 67,226

[30] Foreign Application Priority Data Sept. 1, 1969 Nov. 3, 1969Germany ..P 19 44 276.3 Germany ..P 19 55 157.6

[52] U.S. Cl. ..260/368, 260/273 [51] Int. Cl. ..C09b 1/40, C09b 1/42[58] Field of Search ..260/368, 273

[56] References Cited UNITED STATES PATENTS 1,714,249 5/1929 Smith etal. ..260/273 3,194,820 7/1965 Grelat ....260/367 2,068,313 1/1937Dettwyler ..260/368 Primary Examiner-Henry R. Jiles Assistant ExaminerE.Jane Skelly Attorney-Johnston, Root, OKeeffe, Keil, Thompson & Shurtleff1 ABSTRACT 2,2'-diacylamino-l,l'-dianthraquinonyls having the in which Rdenotes alkyl having one to six carbon atoms or substituted orunsubstituted aryl and to a method for the production of the compounds(I). The compounds (I) may be prepared by reaction of l-halo-2-acy1aminoanthraquinones having the formula:

0 Hal in which R has the above meanings and Hal denotes a chlorine orbromine atom with copper powder in a solvent which contains the groupingl -N CO. The compounds (I) represent a valuable intermediate for themanufacture of dyes, e.g. flavanthrene.

5 Claims, N0 Drawings 2,2'-DlACYLAMINO-l ,l '-DIANTHRAQUINONYLS Thisinvention relates tonew 2,2-diacylamino-l,l'- dianthraquinonyls havingthe formula:

RO C-HN V in which R denotes alkyl having one to six carbon atoms orunsubstituted or substituted aryl, and a process for the production ofthese compounds.

The new 2,2'-diacylamino-l,l'-dianthraquinonyls may for example containas alkyl radicals: methyl, ethyl, propyl, butyl or hexyl and as arylradicals for example phenyl. The aryl radical may also containsubstituents such as halogen atoms or low molecular weight alkyl oralkoxy groups. Examples of substituted aryl radicals are:2-chlorophenyl, 3-chlorophenyl, 4- chlorophenyl, 4-methoxyphenyl ormethylphenyl.

Those compounds having the formula (I) which contain an alkyl radicalhaving one to three carbon atoms or the phenyl radical as the radical Rare of special commercial interest.

The new 2,2-diacylamino-l,l'-dianthraquinonyls are valuableintermediates, for example for the production of dyes. Thus for exampleflavanthrene can be prepared particularly advantageously from the new2,2'-diacylamino-l,1-dianthraquinonyls.

The new 2,2'-diacylamino-l,l-dianthraquinonyls are obtained in goodyields when a l-halo-2- acylaminoanthraquinone having the formula:

in which Hal denotes a chlorine or bromine atom, is reacted in a solventwhich contains the grouping -N- CO- with copper powder.

l Examples of solvents which contain the grouping -N- 1 CO- are amidesor imides such as acid amides of secondary amines of whichdimethylformamide or dimethylacetamide are mentioned or heterocycliccompounds such as methylpyrrolidone;

in the new process it is advantageous to use 0.5 to 3 times the weightof the said solvents with reference to l-halo-2-acylaminoanthraquinone.Other inert solvents such as nitrobenzene or a halobenzene may be addedto the solvents specified. Since the reaction mixture becomes mobile inthe course of the reaction, the addition of large amounts of solventdoes not add any advantage.

The most advantageous amount of copper depends on the size of theradical R. As a rule from 20 to 35 .percent by weight based on l-halo-Z-acylaminoanthraquinone is enough.

when

The temperature at which the reaction begins depends on the type ofsolvent. In all cases however it is considerably lower than in similarprior art methods. Thus for example the reaction can be successfullyconcluded in dimethylformamide at only C. The temperature used isgenerally from 50 C to the boiling point of the solvent, preferably from60 C to 130 C.

Particularly pure compounds having the formula (I) are obtained in asmooth reaction and with high yields the reaction of the l-halo-2-acylaminoanthraquinones having the formula (II) with copper powder inthe solvents of the said type is carried out at temperatures below 50 C.to room temperature. As the rate of reaction naturally falls as thetemperature falls, it is recommended that the reaction should be carriedout in the presence of a small amount of halogen. In this way thereaction is completely concluded in a short time at only roomtemperature. Small amounts of halogen may be for example 0.25 to 2parts.

by weight of chlorine, bromine or iodine based on parts by weight of thecompound having the formula (ll).

This method of producing 2,2-diacrylamino-l ,1 -dianthraquinonyls isparticularly preferred because of its technical advantages and at thesame time its very pure reaction product.

The procedure in the production of the new2,2'-diacylamino-Ll'-dianthraquinonyls may be for example that thecopper powder and solvent are placed in a vessel and thel-halo-2-acylamino compound is added at moderately elevated temperature.It is most advantageous however to place the l-halo-2-acylamino compoundwith the solvent in a vessel and to control the exothermic reaction byadding copper powder in portions. Both components may however also beadded to the solvent and the reaction initiated by cautious heating. Thetemperature then rises spontaneously, in some cases up to the boilingpoint of the solvent, and if necessary may be checked by cooling.

The working up of the reaction products is very simple. The desireddianthraquinonyl either separates during the reaction or upon coolingand is isolated by filtration. After conventional decoppering withhydrochloric acid and chlorate according to the Ullmann reaction, thedesired compounds are obtained in a pure form as yellow to yellowishbrown substances having a melting point above 300 C.

The smooth formation of the new 2,2'-diacylaminol,l '-dianthraquinonylsby the said method is surprising because for example it does not occurwhen the starting materials are exposed to the conditions under which2,2'-diacylamino-l ,1 -dianthraquinonyls of dibasic carboxylic acidssuch as phthalic acid are prepared from the correspondingl-halo-2-acylaminoanthraquinones. In this prior art method (Fiat FinalReport, 1313, volume II, 175, and BIOS Report, 987, 34) the solventsused are nitrobenzene, naphthalene or .trichlorobenzene. Under theseknown conditions, the halogen atom in the l-position is eliminated fromthe starting material having the formula (ll) without the desireddimerization taking place. Compounds having the formula (ll) readilyeliminate their halogen atoms as those skilled in the art known (seeJ.Chem.Soc., 2l61 (1951)).

The following Examples illustrate the invention. The parts specified inthe Examples are parts by weight.

EXAMPLE 1 100 parts of l-chloro-2-acetaminoanthraquinone (obtained byacylation of 1-chloro-2-aminoanthraquinone with acetic anhydride oracetyl chloride in nitrobenzene) is heated to 70 C in 150 parts ofdimethylformamide. 29 parts of copper powder is added and the whole isstirred for 8 hours at 70C, and then cooled to room temperature. The2,2- diacetylamino-1,1'-dianthraquinonyl formed is suction filtered andwashed with 100 parts of cold dimethylformamide. After conventionaldecoppering, 72 parts of the new compound is obtained which vats with ared color and melts at 360 C.

When nitrobenzene or trichlorobenzene is used as solvent instead ofdimethylformamide, unchanged 1- chloro-2-acetaminoanthraquinone isrecovered at the said temperature of 70 C.

EXAMPLE 2 EXAMPLE 3 200 parts of dimethylformamide, 35 parts of copperpowder and 105 parts of lchloro-2- propionylaminoanthraquinone areheated to 90 C. After the reaction has commenced, heatingisdiscontinued. The temperature rises spontaneously to the boiling pointof the solvent. The reaction is complete after boiling has taken placefor one hour. The whole is cooled and worked up as already described.The yield is 68 parts of 2,2'-dipropionylamino-l,1 -dianthraquinonylhaving a melting point of 345 to 350 C. The compound vats with a redcolor.

EXAMPLE 4 300 parts of N-methylpyrrolidone and 100 parts of l-'chloro-2-acetaminoanthraquinone are heated to 80 C. 30 parts of copperpowder is added in the course of 1 hour at this temperature. Afterhaving been stirred for 6 hours at from 80 to 85 C, the whole is cooledand worked up in the usual way. 58 parts of the same product as inExample 1 is obtained.

EXAMPLE 100 parts of 1-chloro-2-benzoy1aminoanthraquinone is introducedinto 150 parts of dimethylformamide at 80 C. 23 parts of copper powderis added and the whole is stirred at from to C for 8 hours, and allowedto cool overnight. The product is suction filtered and washed with partsof dimethylformamide. lt is decoppered as usual and 54 parts of 2,2-dibenzoylaminol ,1 '-dianthraquinonyl having a melting point of 322 to326 C is obtained. The compound vats with a red color.

EXAMPLE 6 4.8 parts of l-chloro-2-acetaminoanthraquinone is stirred into7.2 parts of anhydrous dimethylformamide at room temperature. 1.15 partsof copper powder and 1 percent (with reference to l-chloro-2-acetaminoanthraquinone) of bromine are added. The reaction beginsimmediately. The whole is stirred for 8 hours at 22 to 35 C, suctionfiltered, washed with dimethylformamide and decoppering is carried outwith chlorate and hydrochloric acid. 3.74 parts of 2,2-diacetylamino-l,1'-dianthraquinonyl having a melting point of 367 to 369C is obtained, i.e., 88 percent of the theory.

EXAMPLE 7 4.8 parts of l-chloro-2-acetaminoanthraquinone is stirred into7.2 parts of dimethylformamide with 1.2 parts of copper powder and 0.048part of iodine at 35 to 40 C for 3 hours. The product is worked up as inExample 6 and 3.62 parts of 2,2'-diacetylamino-l,1'-dianthraquinonyl (86percent of the theory) is obtained.

When the procedure of Example 6 or Example 7 is repeated but withoutadding a halogen and while stirring for 7 hours at 35 to 40 C, similarresults are obtained.

1 claim:

1. A 2,2-diacylamino-l,1-dianthraquinonyl having the formula in which Rdenotes alkyl having one to six carbon atoms, phenyl or phenylsubstituted by chloro, lower alkyl or lower alkoxy.

2. A 2,2'-diacylamino-l,l'-dianthraquinonyl having the formula (I) inclaim 1 in which R is a radical selected from the group consisting ofmethyl, ethyl, propyl, butyl, hexyl, phenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 4-methoxyphenyl and 4- methylphenyl.

3. 2,2'-diacetylamino-l,1'-dianthraquinonyl.

4. 2,2-dipropionylamino-l,1'-dianthraquinonyl.

5. 2,2'-dibenzoylamino-l ,l '-dianthraquinony1.

l l i i

2. A 2,2''-diacylamino-1,1''-dianthraquinonyl having the formula (I) inclaim 1 in which R is a radical selected from the group consisting ofmethyl, ethyl, propyl, butyl, hexyl, phenyl, 2-chlorophenyl,3-chlorophenyl, 4-chlorophenyl, 4-methoxyphenyl and 4-methylphenyl. 3.2,2''-diacetylamino-1,1''-dianthraquinonyl. 4.2,2''-dipropionylamino-1,1''-dianthraquinonyl. 5.2,2''-dibenzoylamino-1,1''-dianthraquinonyl.